関: benzyl、benzylic

WordNet

the univalent radical derived from toluene (同)benzyl_group, benzyl radical
relating to benzyl

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出典(authority):フリー百科事典『ウィキペディア（Wikipedia）』「2017/05/13 19:32:12」(JST)

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Benzil (systematically known as 1,2-diphenylethane-1,2-dione) is the organic compound with the formula (C₆H₅CO)₂, generally abbreviated (PhCO)₂. This yellow solid is one of the most common diketones. Its main use is as a photoinitiator in polymer chemistry.^[3]

Structure

The compound's most noteworthy structural feature is the long carbon-carbon bond of 1.54 Å, which indicates the absence of pi-bonding between the two carbonyl centers. The PhCO centers are planar, but the pair of benzoyl groups are twisted with respect to the other with a dihedral angle of 117°.^[4] In less hindered analogues (glyoxal, biacetyl, oxalic acid derivatives), the (RCO)₂ group adopts a planar, anti-conformation.

Applications

Most benzil is used in the free-radical curing of polymer networks. Ultraviolet radiation decomposes benzil, generating free-radical species within the material, promoting the formation of cross-links. Benzil is a potent inhibitor of human carboxylesterases, enzymes involved in the hydrolysis of carboxylesters and many clinically used drugs.^[5]

Benzil is a relatively poor photoinitiator, and is seldom used. It absorbs at the 260 nm wavelength. It undergoes photobleaching, which allows the curing light to reach deeper layers of the material on longer exposure.^[6]

Reactions

Benzil is a standard building block in organic synthesis. It condenses with amines to give diketimines ligands. A classic organic reaction of benzil is the benzilic acid rearrangement, in which base catalyses the conversion of benzil to benzilic acid. This reactivity is exploited in the preparation of the drug phenytoin. Benzil also reacts with 1,3-diphenylacetone in an aldol condensation to give tetraphenylcyclopentadienone.

Preparation

Benzil is prepared from benzoin, for example with copper(II) acetate:^[7]

PhC(O)CH(OH)Ph + 2 Cu²⁺ → PhC(O)C(O)Ph + 2 H⁺ + 2 Cu⁺

Other suitable oxidizing agents such as nitric acid (HNO₃) are used routinely.

Iron(III) chloride (FeCl₃) can be used as an inexpensive catalyst for this chemical conversion.^[8]

References

^ Acta Crystallogr. B43 398 (1987)
^ Spectrochim. Acta A60 (8-9) 1805 (2004)
^ Hardo Siegel, Manfred Eggersdorfer "Ketones" in Ullmann's Encyclopedia of Industrial Chemistry Wiley-VCH, 2002 by Wiley-VCH, Weinheim. doi:10.1002/14356007.a15_077
^ Quang. Shen, Kolbjoern. Hagen "Gas-phase molecular structure and conformation of benzil as determined by electron diffraction" J. Phys. Chem., 1987, 91 (6), pp 1357–1360. doi:10.1021/j100290a017.
^ Wadkins. R. M. et al "Identification and characterization of novel benzil (diphenylethane-1,2-dione) analogues as inhibitors of mammalian carboxylesterases. J. Med. Chem., 2005 48 pp 2906–15.
^ https://books.google.cz/books?id=b1jRBQAAQBAJ&pg=PA78&dq=benzil+photoinitiator&hl=en&sa=X&redir_esc=y#v=onepage&q=benzil%20photoinitiator&f=false
^ Depreux, P.; Bethegnies, G.; Marcincal-Lefebvre, A. (1988). "Synthesis of benzil from benzoin with copper(II) acetate". Journal of Chemical Education. 65 (6): 553. doi:10.1021/ed065p553.
^ Bi, Xiaoxin; Wu, Lintao; Yan, Chaoguo; Jing, Xiaobi; Zhu, Hongxiang (2011). "One-Pot Synthesis Benzils from Aldehydes Via Nhc-Catalyzed Benzoin Dimerization Under Metal-Free Conditions in Water". Journal of the Chilean Chemical Society. 56 (2): 663. doi:10.4067/S0717-97072011000200008.

English Journal

Changing our culture.

Benzil DL.
Journal of neurosurgery.J Neurosurg.2014 May;120(5):1212-6. doi: 10.3171/2014.1.JNS131318. Epub 2014 Feb 21.
Today, a great challenge of our profession is to envision how we will deliver exemplary neurosurgical care in the future. To accomplish this requires anticipating how economic, political, and societal influences will affect our ability to provide the highest quality of patient care in an arena that
PMID 24559225

A new fluorescent and electrochemical Zn2+ ion sensor based on Schiff base derived from benzil and L-tryptophan.

Dutta K1, Deka RC2, Das DK3.
Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.Spectrochim Acta A Mol Biomol Spectrosc.2014 Apr 24;124:124-9. doi: 10.1016/j.saa.2013.12.090. Epub 2014 Jan 4.
Single molecule acting as both fluorescent and electrochemical sensor for Zn(2+) ion is rare. The product (L) obtained on condensation between benzil and L-tryptophan has been characterized by H NMR, ESI-MS and FT-IR spectroscopy. L in 1:1 (v/v) CH3OH:H2O solution shows fluorescence emission in the
PMID 24468984

Glass transition and mixing thermodynamics of a binary eutectic system.

Tu W1, Chen Z, Gao Y, Li Z, Zhang Y, Liu R, Tian Y, Wang LM.
Physical chemistry chemical physics : PCCP.Phys Chem Chem Phys.2014 Feb 28;16(8):3586-92. doi: 10.1039/c3cp52868e.
A quantitative evaluation of the contribution of mixing thermodynamics to glass transition is performed for a binary eutectic benzil and m-nitroaniline system. The microcalorimetric measurements of the enthalpy of mixing give small and positive values, typically ~200 J mol(-1) for the equimolar mixt
PMID 24413254

Japanese Journal

New Flavan and Benzil Isolated from Fissistigma latifolium

Lan Yu-Hsuan,Peng Yi-Ting,Thang Tran-Dinh [他],Hwang Tsong-Long,Dai Do-Ngoc,Leu Yann-Lii,Lai Wan-Chun,Wu Yang-Chang
Chemical and Pharmaceutical Bulletin 60(2), 280-282, 2012
… Compound 2 is the first report of benzil from Fissistigma species. …
NAID 130001852410

25pPSB-56 ベンジル結晶における光誘起電磁パルスの発生(25pPSB 領域5ポスターセッション(光誘起相転移・励起子・非線形等),領域5(光物性))

岡崎勇樹,長谷川尊之,高木芳弘
日本物理学会講演概要集 65(2-4), 738, 2010-08-18
NAID 110008099237

Asymmetric Reduction of Benzil to (S)-Benzoin with Penicillium claviforme IAM 7294 in a Liquid-Liquid Interface Bioreactor (L-L IBR)

Oda Shinobu,Isshiki Kunio
Bioscience, biotechnology, and biochemistry 72(5), 1364-1367, 2008-05-23
The asymmetric reduction of benzyl to (<I>S</I>)-benzoin with <I>Penicillium claviforme</I> IAM 7294 was applied to a liquid-liquid interface bioreactor (L-L IBR) using a uniqu …
NAID 10027528144

Related Pictures

★リンクテーブル★

リンク元	「benzylic」「benzyl」
拡張検索	「3-quinuclidinyl benzilate」「propylbenzilylcholine mustard」「benzilate」

「benzylic」

Benzil
Names
	Preferred IUPAC name Diphenylethanedione
	Systematic IUPAC name 1,2-Diphenylethane-1,2-dione
	Other names Diphenylethane-1,2-dione; Benzil; Dibenzoyl; Bibenzoyl; Diphenylglyoxal
Identifiers
CAS Number	134-81-6 ;
3D model (Jmol)	Interactive image; Interactive image;
ChEBI	CHEBI:51507 ;
ChemSpider	8329 ;
ECHA InfoCard	100.004.689
PubChem CID	8651;
	InChI InChI=1S/C14H10O2/c15-13(11-7-3-1-4-8-11)14(16)12-9-5-2-6-10-12/h1-10H Key: WURBFLDFSFBTLW-UHFFFAOYSA-N ; InChI=1/C14H10O2/c15-13(11-7-3-1-4-8-11)14(16)12-9-5-2-6-10-12/h1-10H Key: WURBFLDFSFBTLW-UHFFFAOYAZ ;
	SMILES O=C(C(=O)c1ccccc1)c2ccccc2 ; c1ccc(cc1)C(=O)C(=O)c2ccccc2 ;
Properties
Chemical formula	C14H10O2
Molar mass	210.23 g·mol−1
Appearance	yellow crystals or powder
Density	1.23 g/cm3, solid (1.255 g/cm3, x-ray)
Melting point	94.0 to 96.0 °C; 201.2 to 204.8 °F; 367.1 to 369.2 K
Boiling point	346.0 to 348.0 °C; 654.8 to 658.4 °F; 619.1 to 621.1 K
Solubility in water	insoluble
Solubility in ethanol	soluble
Solubility in diethyl ether	soluble
Solubility in benzene	soluble
Magnetic susceptibility (χ)	-118.6·10−6 cm3/mol
Structure
Crystal structure	P31,221
Dipole moment	3.8 D
Hazards
Main hazards	Irritant
NFPA 704	1 2 0
Related compounds
Related diketones	biacetyl
Related compounds	benzophenone; glyoxal; bibenzil
	Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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	Infobox references

　　[★]

ベンジリック、ベンジルの

関: benzil、benzyl

「benzyl」

　　[★]

ベンジル

関: benzil、benzylic

「3-quinuclidinyl benzilate」

　　[★]

3-キヌクリジニルベンジラート、3-キヌクリジニルベンジレート

「propylbenzilylcholine mustard」

　　[★]

プロピルベンジリルコリンマスタード

「benzilate」

　　[★]

ベンジル酸、ベンジラート

[1] Acta Crystallogr. B43 398 (1987)

[2] Spectrochim. Acta A60 (8-9) 1805 (2004)

[Ullmann-3] Hardo Siegel, Manfred Eggersdorfer "Ketones" in Ullmann's Encyclopedia of Industrial Chemistry Wiley-VCH, 2002 by Wiley-VCH, Weinheim. doi:10.1002/14356007.a15_077

[4] Quang. Shen, Kolbjoern. Hagen "Gas-phase molecular structure and conformation of benzil as determined by electron diffraction" J. Phys. Chem., 1987, 91 (6), pp 1357–1360. doi:10.1021/j100290a017.

[5] Wadkins. R. M. et al "Identification and characterization of novel benzil (diphenylethane-1,2-dione) analogues as inhibitors of mammalian carboxylesterases. J. Med. Chem., 2005 48 pp 2906–15.

[6] ttps://books.google.cz/books?id=b1jRBQAAQBAJ&pg=PA78&dq=benzil+photoinitiator&hl=en&sa=X&redir_esc=y#v=onepage&q=benzil%20photoinitiator&f=false

[7] Depreux, P.; Bethegnies, G.; Marcincal-Lefebvre, A. (1988). "Synthesis of benzil from benzoin with copper(II) acetate". Journal of Chemical Education. 65 (6): 553. doi:10.1021/ed065p553.

[8] Bi, Xiaoxin; Wu, Lintao; Yan, Chaoguo; Jing, Xiaobi; Zhu, Hongxiang (2011). "One-Pot Synthesis Benzils from Aldehydes Via Nhc-Catalyzed Benzoin Dimerization Under Metal-Free Conditions in Water". Journal of the Chilean Chemical Society. 56 (2): 663. doi:10.4067/S0717-97072011000200008.

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案内

案内

benzil